Ring halogen-free substituted triazine compounds as bleach activators

ABSTRACT

Ring halogen-free substituted triazine compounds of the formula   WHERE A is a radical selected from pyridinium, dialkoxyphosphinyl, mercapto, (dialkylthiocarbamoyl)thio, alkyl sulfonyl, trihalomethyl and sulfophenoxy radicals; and R1 and R2 individually represent hydroxy, mercapto, alkyl, alkenyl, alkoxy, alkylmercapto, aryl, aryloxy, arylmercapto, dialkoxyphosphinyl or   where R3 and R4 may be hydrogen, alkyl, cyanoalkyl, hydroxyalkyl, carboxyalkyl, chloroalkyl, alkoxyalkyl, sulfoalkyl, aryl, sulfoaryl, acylaminoaryl or carbamoylalkyl, or where R3 and R4 taken together may be joined to complete a heterocyclic ring selected from morpholine, piperazine and piperidine rings; are effective as bleach activators for peroxygen bleaching compositions.

United States Patent Brady et al.

[4 1 Oct. 14, 1975 RING HALOGEN-FREE SUBSTITUTED TRIAZINE COMPOUNDS ASBLEACH ACTIVATORS [75] Inventors: Thomas Eugene Brady, Piscataway;

Frank Fred Loffelman, Somerville, both of NJ.

[73] Assignee: American Cyanamid Company,

Stamford, Conn.

[22] Filed: Mar. 21, 1973 [21] Appl. No.: 343,575

Primary Examiner-Benjamin R. Padgett Assistant ExaminerB. Hunt Attorney,Agent, or FirmJohn L. Sullivan [57] ABSTRACT Ring halogen-freesubstituted triazine compounds of the formula where A is a radicalselected from pyridinium, dialkoxyphosphinyl, mercapto,(dialkylthiocarbamoyl)thio, alkyl sulfonyl, trihalomethyl andsulfophenoxy radicals; and R and R individually represent hydroxy,mercapto, alkyl, alkenyl, alkoxy, alkylmercapto, aryl, aryloxy,arylmercapto, dialkoxyphosphinyl where R and R may be hydrogen, alkyl,cyanoalkyl, hydroxyalkyl, carboxyalkyl, chloroalkyl, alkoxyalkyl,sulfoalkyl, aryl, sulfoaryl, acylaminoaryl or carbamoylalkyl, or where Rand R taken together may be joined to complete a heterocyclic ringselected from morpholine, piperazine and piperidine rings; are effectiveas bleach activators for peroxygen bleaching compositions,

10 Claims, No Drawings RING HALOGEN-FREE SUBSTITUTED TRIAZINE COMPOUNDSAS BLEACH ACTIVATORS This invention relates to bleaching compositionsand more particularly to improved bleaching compositions comprisinghydrogen peroxide or a hydrogen peroxidereleasing compound and as anactivator for the peroxide-releasing compound a ring halogen-freetriazine derivative represented by the formula:

ll a-A where A is a radical selected from pyridinium,dialkoxyphosphinyl, mercapto, (dialkylthiocarbamoyl) thio, alkylsulfonyl, trihalomethyl and sulfophenoxy radicals; and R and Rindividually represent hydroxy, mercapto, alkyl, alkenyl, alkoxy,alkylmercapto, aryl, aryloxy, arylmercapto, dialkoxyphosphinyl or whereR and R may be hydrogen, alkyl, cyanoalkyl, hydroxyalkyl, carboxyalkyl,chloroalkyl, alkoxyalkyl, sulfoalkyl, aryl, sulfoaryl, acylaminoaryl orcarbamoylalkyl, or where R and R taken together may be joined tocomplete a heterocyclic ring selected from morpholine, piperazine andpiperidine rings. In each instance where alkyl, alkenyl or alkoxy ismentioned, the term is intended to designate lower (i.e., C -C alkyl,lower (i.e., C -C alkenyl or lower (i.e., C -C )alk0xy.

Although the ring halogen-free triazine derivatives defined by the aboveformula are derivatives of striazines, similarly substituted derivativesof unsymmetrical triazine rings are also contemplated as activators forthe bleach composition of the invention.

Typical halogen-free triazine compounds useful as bleach activators inthe bleach compositions of this invention are the following.

OCH

Ila

l man),

Lon

l CCh Thebleaching compositions of the invention contain the activatingcompound and the hydrogen peroxidereleasing compound in a molar ratioranging from about 1:1 to about 1:10, respectively, with a preferredrange of about 1:1 to l:3. The actual ratio of activator to bleach can',of course, be varied widely for varying applications.

The oxygen bleaches useful in these bleaching compositions are hydrogenperoxide and organic peroxides and inorganic peroxygen salts thatliberate hydrogen peroxide in water. Examples of peroxide bleachingcompounds are urea peroxide, benzoyl peroxide, methyl ethyl ketoneperoxide, and the like. Examples of inorganic peroxygen bleachingcompounds are alkali metal perborates, percarbonates, perphosphates,persulfates, monopersulfates, and the like. Mixtures of two or morebleaching compounds can, of course, be used if desired.

Although the various peroxide releasing compounds as mentioned above maybe used in the compositions of the invention, preferredperoxide-releasing compounds are sodium perborate (for economicconsiderations) and sodium percarbonate (for ecological considerations).

The activated bleach compositions of the invention are useful for bleachapplications for various substrates including fabrics, particularly whenincorporated with stains. including food stains such as those of coffee,tea,

. stains and the like.

wine and the like as well as to maintain purity of white in uncoloredtextiles. Aside from food stains, soiling in general may be removed suchas grass stains, urine In addition to the detergent, peroxygen-releasingcompound and peroxygen bleach activator, such detergent compositions maycontain other optional additives such as germicides, fungicides,enzymes, optical brighteners, colorants, perfumes, thickeners, emulsionor suspension stabilizers, and the like, including builders," such assodium phosphate, salts, carbonates, silicates, and the like as usuallyencountered in the art.

The detergent component of such activated bleach compositions may be anyof the conventional types such as anionic, cationic, nonionic oramphoteric.

Examples of typically suitable anionic detergents include the alkalimetal or alkaline earth metal salts of higher alkylbenzene sulfonates,olefin, sulfonates,

higher alkyl sulfates and higher fatty acid monoglycer- Ex. idesulfates. No. R, R Yield M.P.

Examples of typically suitable cationic detergents in- 1 N(CH2CN)2N(CHZCN)Z 60% 246448 dm clude tetraalkyl ammonium salts in which one ofthe 2 cu o- CH 74% 13s mc. dec. alkyl groups contains approximately 12to 18 carbons 5 3 CHQO N(CH2CN)= 67% such as dodecyltrimethylammoniumchloride or ethyld- Evaluation of Compounds as Bleach Activatelmethyloctadecylammontum methosulfate.

Exam 1 S Suitabl t ical m hoteri d t r ts The compounds of Examples l-3,plus additional p e o y yp a p c e e gen compounds (Examples 4-6) wereevaluated as activaare those detergent compounds possessing bothcattonic and anionic sites and include, for example, amino l torsapplied wlth and detergemf In fan acids such as dimeth lamino r0 ionicacid and the tests, the mole ratio of activator used to sodium 3 Y P Pperborate was l:l.1. tmlnodifatty actds such as methyltmmodllaurtc acid.

The test procedure was as follows: Five-gram Examples of typicalnoniontc detergents inclu d swatches of desized, 80 X 80 cotton fabricare stained polyglycolethers ofalkanolamides ofhigher fatty acids 5 withtea in the following maImeL Five tea bags are and aiscf poiygiycoiethers of higher aikanois and higher I placed in one liter of water andboiled for five minutes. fatty acids' The swatches are then immersed inthe tea and the boil- Bieaching compositions y gonei'aiiy be used aisoing is continued for another five minutes. The swatches for theirgermicidal properties in various applications are then removed from thetea wrung out dried at for oomli'oi of microbial growtii- Applications ybe 200-2l5F., rinsed in cold water and again dried. made to any surfaceor substrate where such control is T f h i d cotton Swatches e l d i adesiredstainless steel Terg-O-Tometer, a test washing ma- The treatmentof swimming pool water and swimchine, manufactured by U.S. TestingCompany and ming pool surfaces with the compositions of the invenused inthe detergent trade for evaluation purposes. tion is especiallyefficacious since the usually lower Forty grams of unstained cottonfabric and one liter of temperatures of these environments preventeffective distilled water at 120F. are then added so as to provide useofother antimicrobial agents. A related utility is the a typicalhousehold washing machine water to cloth treatment of water supplies torender the same fit for ratio of about 20:1. There are then added 2.0grams of human consumption or for industrial use, such as the Tide" (ananionic alkylaryl sulfonate type detergent), sanitization of field waterfor consumption by military 0.33 gram of anhydrous sodium perborate (oran equivpersonnel or the treatment of industrial process water alent ofhydrated material) and the indicated amount so it can be reused inindustrial processes or by the surof the activator compound. TheTerg-O-Tometer is oprounding community. The compositions also may beerated at 100 cycles per minute for fifteen minutes at employed inadmixture with detergents for use as home a temperature of 120F. Theswatches are then reor industrial germicidal detergents, or in hairbleaching moved, rinsed with cold water, and dried at roomtemcompositions containing peroxygen compounds. perature.

The following examples and tests will serve to further Reflectancereadings On the w che are aken both ill h i i before and afterlaundering using a Hunter Model 25-M Reflectometer with a blue filter.The swatches EXAMPLES are backed with a white procelain plate and readonce on each side. Fluorescent effect is excluded from all Preparationof Pyridinium Compounds readings- The reflectance readings are averagedand the percent stain removal is obtained in accordance with thefollowing formula in which R is the symbol for Reflec- Total R(bleached) minus R (stained) v Cl stain removal R (unstained) minus R(stained) 100 Control runs are also made for each set or series of R2evaluation tests using detergent and sodium perborate with no activator.The percent stain removed may vary To a solution of the respectivedi-functional monosomewhat on the Control due to variations in the clothchloro triazine in 100 ml. ethyl acetate is added a molar and the teaused to produce the stains. equivalent of pyridine (using a slightexcess). The solid The test results obtained are shown in Table l whereproduct forms almost immediately. The slurry is stirred the activatorcompounds are identified by the A, R for 4 hours, filtered and dried. Norecrystallization is and R radicals thereof in the general formula shownat necessary. the top of the Table.

Table l R Wt. of Ex. 2 Stain Removed Activator Stain No. A R, R(Control) (g.) Removed l N(CH CN) N(CH CN) 35.9 1.10 44.9

TABLE I Continued RI-KNTEA Y Wt. of

Ex. Stain Removed Activator Stain No. A R R; (Control) (g.) Removed 2 -NOCH OCH;, 38.2 0.78 44.2

l 3 N OCH;, -N(CH CN) 42.5 0.96 50.5

"Prepared according to J. Org. Chem. 22. 444 (I957) Prepared accordingto 1.08. 1967. C. 466.

We claim: 3. A composition according to claim 1 wherein the l. Ableaching composition Comprising hydrogen hydrogen peroxide-releasingcompound is sodium perperoxide or a hydrogen peroxide-releasing compoundb r t or di -b r and an activating amount ofa ring halogen-free triazine4. A composition according to claim 1 wherein A in compound representedby the formula: the ring halogen-free triazine compound is a pyridiniumradical.

5. A composition according to claim 4 wherein the R --Aring-halogen-free triazine compound is represented by I the formula H,COI-- where A is a radical selected from the group consisting N N Y C19 ofpyridinium, dialkoxyphosphinyl, mercapto, (dialkylthiocarbamoy1)thio,alkyl sulfonyl, trihalomethyl and sulfophenoxy radicals; and R and R areindividually selected from the group consisting of hydroxy, mercapto,alkyl, alkenyl, alkoxy, alkylmercapto, aryl, aryloxy, arylmercapto,dialkoxyphosphinyl and 6. A composition according to claim 4 wherein thering halogen-free triazine compound is represented by the formula whereR, and R are individually selected from the group consisting ofhydrogen, alkyl, cyanoalkyl, hy- N 69 I droxyalkyl, carboxyalkyl,chloroalkyl, alkoxyalkyl, (NCCHZ)2N I/ \F sulfoalkyl, aryl, sulfoaryl,acylaminoalkyl and carbal moylalkyl, and where R and R taken togetherare 0 N N joined to complete a heterocyclic ring selected from V thegroup consisting of morpholine, piperazine and Cle piperidine rings.N(CHCN 2. A composition according to claim 1 wherein the mole ratio ofthe ring halogen-free triazine compound 7, A composition di to l i 4 h ih to the hydrogen peroxide-releasing compound is from ring halogen-freetriazine compound is represented by about 1:1 to about 1:10. the formula9 N aCO- I HS- -SH I N N N V CH NU-UC H 8, A composition according toclaim 1 wherein the 10. A composition according to claim 1 wherein thering halogen-free triazine compound is represented by ""8 halogen-freemazme compound represented y the formula the formula 3 if N CH3O), |4(OCHQ, 4 I -0- so n I NV" N N O=P(OCH so,H.

9. A composition according to claim 1 wherein the ring halogen-freetriazine compound is represented by th? formula

1. A BLEACHING COMPOSITION COMPRISING HYDROGEN PEROXIDE OR A HYDROGENPEROXIDE-RELEASING COMPOUND AND AN ACTIVATING AMOUNT OF A RINGHALOGEN-FREE TRAZINE COMPOUND REPRESENTED BY THE FORMULA:
 2. Acomposition according to claim 1 wherein the mole ratio of the ringhalogen-free triazine compound to the hydrogen peroxide-releasingcompound is from about 1:1 to about 1:10.
 3. A composition according toclaim 1 wherein the hydrogen peroxide-releasing compound is sodiumperborate or sodium percarbonate.
 4. A composition according to claim 1wherein A in the ring halogen-free triazine compound is a pyridiniumradical.
 5. A composition according to claim 4 wherein thering-halogen-free triazine compound is represented by the formula
 6. Acomposition according to claim 4 wherein the ring halogen-free triazinecompound is represented by the formula
 7. A composition according toclaim 4 wherein the ring halogen-free triazine compound is representedby the formula
 8. A composition according to claim 1 wherein the ringhalogen-free triazine compound is represented by the formula
 9. Acomposition according to claim 1 wherein the ring halogen-free triazinecompound is represented by the formula
 10. A composition according toclaim 1 wherein the ring halogen-free triazine compound is representedby the formula